Extended Structures Built on the Triphenoxymethane Platform: Modeling Metalloenzyme Active Sites

无机，生物无机和有机化学计划的这一奖项支持了佛罗里达大学Michael Scott教授的研究，以开发具有将金属离子保持在附近的能力的氮供体配体，以促进催化过程中的协同性并模拟金属酶活性位点。 将氨基酸基团掺入三苯氧基甲烷平台上，这些构建体将用于反应性和结合研究。 类似于在多铜氧化酶和金属磷酸酶中发现的三核金属催化剂，将合成三核Zn（II）、Cu（II）和Cu（I）化合物的几个不同实例。 使用三苯氧甲烷，也正在努力构建具有三个肽臂的小配体。 当氨基酸基团连接到三苯氧基甲烷时，该平台产生高度的溶解度和有利的臂内氢键接触以及基团的预组织，以促进金属与三个臂的结合，并将手性氨基酸的重要性质赋予金属中心。 这些相同的配体也将用于制备用于水解磷酸酯如RNA的三金属催化剂，因为用于RNA水解的序列选择性催化剂在体外和体内基因技术中具有许多重要的潜在应用。将开发多铜氧化酶的功能模型，多铜氧化酶是主要在高级真核细胞中发现的利用氧的酶的极其重要的家族，尤其是植物、真菌和脊椎动物，并且都用于底物的单电子氧化。 学生将在有机和无机合成和表征方法方面具有很强的背景，并且还将熟练掌握晶体学数据的收集和细化。 合作，以增加女学生和学生的参与，从历史上的黑人大学在本科生和研究生研究计划在佛罗里达大学允许教师和学生从林肯大学参加这项研究在夏季。 PI管理的普通REU课程的学生，包括法国和美国的学生，也将在为期三个月的暑期逗留期间参与这项研究。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Michael Scott at the University of Florida to develop nitrogen donor ligands with the ability to hold metal ions in proximity to foster cooperativity during catalysis and to mimic metalloenzyme active sites. Amino acid groups will be incorporated onto the triphenoxymethane platform and these constructs will be used for both reactivity and binding studies. In analogy to the trinuclear metal catalysts found in multi-copper oxidases and metallophosphatases, several different examples of trinuclear Zn(II), Cu(II), and Cu(I) compounds will be synthesized. Using the triphenoxymethanes, an effort is also underway to build small ligands with three peptide arms. When amino acid groups are attached to triphenoxymethanes, the platform engenders a high degree of solubility and favorable intra-arm hydrogen-bonding contacts and the pre-organization of the groups to facilitate the binding of metals to the three arms and impart the important properties of chiral amino acids onto the metal centers. These same ligands will also be used to prepare trimetallic catalysts for the hydrolysis of phosphate esters such as RNA, since sequence selective catalysts for RNA hydrolysis have many important potential applications in in vitro and in vivo gene technology.Functional models will be developed for multi-copper oxidases, which are an extremely important family of oxygen-utilizing enzymes that are primarily found in higher order eukaryotic cells, especially plants, fungi, and vertebrates, and all are used for single electron oxidations of substrates. Students will develop a strong background in both organic and inorganic synthesis and characterization methods and will also become skilled at the collection and refinement of crystallographic data. A collaboration to increase the participation of female students and students from historically black colleges in the undergraduate and graduate research programs at the University of Florida allows faculty and students from Lincoln University to participate in this research during the summer. The students in the normal REU programs administered by the PI, both French and American, also will be involved in this research during their three-month summer stay.